Retardation film, composition, method of manufacturing retardation film, polarizing plate and liquid crystal display device

ABSTRACT

An object of the present invention is to provide a film capable of giving a necessary retardation without degrading the contrast. The present invention provides a retardation film formed from a composition which includes a polymer compound, a rod-like liquid crystal compound and a photo-reactive compound, wherein the polymer compound has a side chain which has one or more azo groups and/or cynnamate groups, and 3 or more and 10 or less arylene groups; the side chain further has an optionally substituted amino group, or a hydrocarbon group at the terminal; an absolute value of difference between an SP value of the polymer compound and an SP value of the photo-reactive compound is 1.1 or less; and an in-plane retardation of the film at wavelength of 550 nm is 10 nm or more and 200 nm or less.

CROSS-REFERENCE TO RELAYED APPLICATIONS

This patent application is a divisional patent application of U.S.patent application Ser. No. 14/886,740, filed Oct. 19, 2015, whichclaims priorities under 35 U.S.C. §119 to Japanese Patent ApplicationNo. 2014-213749 filed Oct. 20, 2014 and Japanese Patent Application No.2014-214404 filed Oct. 21, 2014. The above applications are herebyexpressly incorporated by reference, in their entirety, into the presentapplication.

TECHNICAL FIELD

This invention relates to a retardation film, a composition, a method ofmanufacturing a retardation film, a polarizing plate and a liquidcrystal display device.

BACKGROUND ART

Liquid crystal display device, recognized as a low-power-consumption,space-saving image display device, has been expanding its applicationsyear by year. As the market expands, not only within television or thelike where high-definition image is required, but also into mobiledevices including mobile phone and tablet personal computer, there hasbeen an increasing need for thinning. The liquid crystal display deviceis configured by a liquid crystal cell, and polarizing plates disposedon both sides thereof. In many cases, the polarizing plate is opticallycompensated while laminated with a retardation film.

Patent Document 1 describes an optical sheet which includes aretardation film having an Nz value exceeding 0.4 and less than 0.6, and(nx−ny)d of 200 to 350 nm, and a transparent layer formed on one surfacethereof, having a thickness of 10 μm or less, and a refractive indexanisotropy given by nx ny≈nz, where nz is refractive index observed inthe thicknesswise direction defined as the Z axis, nx is refractiveindex observed in one direction in a plane normal to the Z axis, ny isrefractive index observed in the direction normal to the Z axis and theX axis, the X axis is laid in the direction in plane along which therefractive index appears maximum, Nz=(nx−nz)/(nx−ny) holds, and d is thefilm thickness.

Patent Document 2 describes a composite retardation plate configured byusing one or two or more sheets of a retardation film having at leastone of nx, ny and nz being different from the other, where nx and nybeing in-plane principal refractive indices, nz being refractive indexin the thicknesswise direction, nx≧ny holds; and one or two or moresheets of liquid crystal phase sheet which is composed of a transparentbase having different values of nx, ny and nz, and a liquid crystalpolymer layer provided thereto; wherein the sheets are combined so thatthe retardation film, the transparent base and the liquid crystalpolymer layer will have different wavelength dependence ofbirefringence, the retardation film and the transparent base will havedifferent values of Nz which is defined by (nx−nz)/(nx−ny); and each ofthe retardation film and the transparent base is composed of a filmhaving a non-liquid crystalline polymer aligned therein.

Patent Document 3 describes a light absorption anisotropic filmcontaining at least one species of thermotropic liquid crystallinedichroic dye, and at least one species of thermotropic liquidcrystalline polymer, wherein the mass content of the thermotropic liquidcrystalline dichroic dye in the light absorption anisotropic film is 30%or more.

CITATION LIST Patent Literature [Patent Document 1] JP-A-2002-107541[Patent Document 2] JP-A-2001-042127 [Patent Document 3]JP-A-2011-237513 SUMMARY OF THE INVENTION

It would be advantageous if a necessary retardation can be achievedsimply by a liquid crystal layer having a large birefringence, so as tomeet the above-described need for the thinning of liquid crystal displaydevice. Nematic liquid crystal layer has, however, been suffering fromdegradation in contrast. This invention was conceived in view of thesituation described above, and is to provide a film capable of giving anecessary retardation without degrading the contrast. This invention isalso to provide a retardation film capable of satisfying desired opticalcharacteristics. This invention is also to provide a composition usedfor manufacturing the retardation film, a method of manufacturing aretardation film, a polarizing plate and a liquid crystal displaydevice.

After intensive studies aimed at solving the problems, the presentinventors found that a retardation film, whose problems have beensolved, may be manufactured by using a polymer compound having a sidechain with certain structure, a rod-like liquid crystal compound andcertain photo-reactive compound. After further intensive studies aimedat solving the problems, the present inventors also found that aretardation film, whose problems have been solved, may be manufacturedby using a polymer compound having a side chain with certain structure,and an alignment controlling agent. This invention was completed basedon these findings. According to this invention, aspects of the inventionbelow will be provided.

(1) A retardation film formed from a composition which comprises apolymer compound, a rod-like liquid crystal compound and aphoto-reactive compound, wherein the polymer compound has a side chainwhich has one or more azo groups and/or cynnamate groups, and 3 or moreand 10 or less arylene groups; the side chain further has an optionallysubstituted amino group, or a hydrocarbon group at the terminal; anabsolute value of difference between an SP value of the polymer compoundand an SP value of the photo-reactive compound is 1.1 or less; and anin-plane retardation of the film at wavelength of 550 nm is 10 nm ormore and 200 nm or less.(2) The retardation film of (1), wherein the polymer compound isrepresented by Formula IX:

in the formula, R¹ represents a hydrogen atom or methyl group, Lrepresents a single bond, —(CH₂)_(x)O— or —(CH₂CH₂O)_(y)—, x is aninteger of 2 to 10, y is an integer of 1 to 5, R² represents anoptionally substituted amino group or hydrocarbon group, and Mrepresents a structure represented by Formula X below:

in the formula, each * represents a bonding site with L or R²; Yrepresents an azo group, —OCO—, —CO(═O)—, —OCO—CH═CH— or —CH═CH—CO₂—, mrepresents an integer of 2 to 9, the plurality of (Y)s may be same ordifferent; and Ar represents an optionally substituted arylene group.(3) The retardation film of (1), wherein a content of the rod-likeliquid crystal compound, relative to 100 parts by mass of the polymercompound, is 0.1 to 40 parts by mass.(4) The retardation film of (1), wherein a content of the photo-reactivecompound, relative to 100 parts by mass of the polymer compound, is 0.1to 40 parts by mass.(5) The retardation film of (1), which is a single layered film.(6) The retardation film of (1), which has an Nz of 0.3 to 0.9, whereNz=(nx−nz)/(nx−ny), nx represents refractive index in in-plane slow axisdirection, ny represents refractive index in the in-plane directionnormal to nx, and nz represents refractive index in the direction normalto nx and ny.(7) The retardation film of (1), which has a thickness of 5 μm or less.(8) A composition comprising a polymer compound, a rod-like liquidcrystal compound and a photo-reactive compound, wherein the polymercompound has a side chain which has one or more azo groups and/orcynnamate groups, and 3 or more and 10 or less arylene groups; the sidechain further has an optionally substituted amino group, or ahydrocarbon group at the terminal; and an absolute value of differencebetween an SP value of the polymer compound and an SP value of thephoto-reactive compound is 1.1 or less.(9) A method of manufacturing a retardation film of (1), which comprisescoating the composition of (8) on a substrate.(10) The method of manufacturing a retardation film according to (9),which further comprises heating the composition, having been coated onthe substrate, at 40° C. or above, and photo-irradiating the compositionafter heating at a dose of 300 to 30000 mJ/cm².(11) A polarizing plate comprising a polarizer, and the retardation filmof (1).(12) A liquid crystal display device comprising the retardation film of(1).(13) The liquid crystal display device of (12), which is an IPS liquidcrystal display device.(14) A retardation film comprising a polymer compound and an alignmentcontrolling agent, wherein the polymer compound has a side chain whichhas one or more azo groups and/or cynnamate groups and 3 or more and 10or less of arylene group, the side chain further has an optionallysubstituted amino group, or a hydrocarbon group at the terminal, acontent of the polymer compound in the retardation film is 71% by massor more, and an in-plane retardation of the film at wavelength of 550 nmis 10 nm or more and 200 nm or less.(15) The retardation film of (14), wherein the polymer compound is acompound represented by Formula IX:

in the formula, R¹ represents a hydrogen atom or methyl group, Lrepresents a single bond, —(CH₂)_(x)O— or —(CH₂CH₂O)_(y)—, x is aninteger of 2 to 10, y is an integer of 1 to 5, R² represents anoptionally substituted amino group or hydrocarbon group, and Mrepresents a structure represented by Formula X below:

in the formula, each * represents a bonding site with L or R²; Yrepresents an azo group, —OCO—, —CO(═O)—, —OCO—CH═CH— or —CH═CH—CO₂—, mrepresents an integer of 2 to 9, the plurality of (Y)s may be same ordifferent; and Ar represents an optionally substituted arylene group.(16) The retardation film of (14), wherein the alignment controllingagent is a compound represented by Formula I below:

in the formula, each R²⁰¹ independently represents an aromatichydrocarbon ring or heterocycle having substituent(s) at least on any ofthe ortho, meta and para positions, each X²⁰¹ independently represents asingle bond or —NR²⁰²—, each R²⁰² independently represents a hydrogenatom, or alkyl group, alkenyl group, aromatic hydrocarbon cyclic groupor heterocyclic group, which may be substituted or unsubstituted.(17) The retardation film of (14), wherein a content of the alignmentcontrolling agent, relative to 100 parts by mass of the polymercompound, is 0.1 to 20 parts by mass.(18) The retardation film of (14), which is a single layered film.(19) The retardation film of (14), which has an Nz value of −0.29 to0.29;where, Nz=(nx−nz)/(nx−ny), nx represents refractive index in in-planeslow axis direction, ny represents refractive index in an in-planedirection normal to nx, and nz represents refractive index normal to nxand ny.(20) The retardation film of (14), which has a thickness of 5 μm orless.(21) A composition comprising a polymer compound and an alignmentcontrolling agent, wherein the polymer compound has a side chain whichhas one or more azo groups and/or cynnamate groups, and 3 or more and 10or less arylene groups; the side chain further has an optionallysubstituted amino group, or a hydrocarbon group at the terminal; and acontent of the polymer compound in the composition is 71% by mass ormore relative to the total solid content.(22) A method of manufacturing a retardation film of (14), whichcomprises coating the composition of (21) over a substrate.(23) The method of manufacturing a retardation film according to (22),which further comprises heating the composition, having been coated onthe substrate, at 40° C. or above, and photo-irradiating the compositionafter heating at a dose of 300 to 30000 mJ/cm².(24) A polarizing plate comprising a polarizer, and the retardation filmof (14).(25) A liquid crystal display device comprising the retardation film of(14).(26) The liquid crystal display device of (25), which is an IPS liquidcrystal display device.

This invention now makes it possible to provide a retardation filmcapable of demonstrating a high contrast and retardation. This inventioncan also provide a retardation film which satisfies desired opticalcharacteristics. By using the composition and the method ofmanufacturing a retardation film of this invention, it now becomespossible to manufacture the retardation film of this invention. Thepolarizing plate and the liquid crystal display device of this inventionshow a high contrast.

DESCRIPTION OF EMBODIMENTS

This invention will be detailed below. In this specification, allnumerical ranges given in the form of “to” preceded and succeeded bynumerals are defined to contain these numerals as the lower and upperlimit values. The solid content in the context of this specificationmeans the solid content measured at 25° C.

In this specification, Re(λ) represents in-plane retardation (nm) atwavelength λ. In this specification, the wavelength λ is 550 nm, unlessotherwise specifically noted. Re(λ) may be measured using KOBRA 21ADH orWR, or KOBRA CCD Series (from Oji Scientific Instruments Co., Ltd.) bymaking light of wavelength 550 nm incident on the film in the directionof the normal line. The retardation may alternatively be measured usingAxoScan (from Axometrics, Inc.).

In this invention, the “slow axis” of the retardation film or the likemeans the direction along which the refractive index appears maximum.The refractive index is measured at a wavelength λ of 550 nm in thevisible region, unless otherwise specifically noted.

In this specification, all numerical values and all numerical ranges,which represent optical characteristics of the individual components,are construed to represent numerical values, numerical ranges andproperties which contain typical errors allowable for the liquid crystaldisplay device and the components used therefor.

In this specification, weight average molecular weight and numberaverage molecular weight are defined by polystyrene equivalent valuesmeasured by gel permeation chromatography (GPC). In this specification,the weight average molecular weight and the number average molecularweight (Mn) may be determined, for example, by using HLC-8220 (fromTosoh Corporation), and TSKgel (registered trademark) column Super AWM-H(from Tosoh Corporation, 6.0 mm ID×15.0 cm), at a column temperature of40° C. Eluent used for the measurement is a 10 mmol/L lithium bromidesolution in NMP (N-methylpyrrolidinone), unless otherwise specificallynoted.

<Retardation Film>

The retardation film of this invention is a retardation film formed froma composition which contains a polymer compound, a rod-like liquidcrystal compound, and a photo-reactive compound. The retardation filmmeans a film showing birefringence over the entire area or a partthereof.

The retardation film of this invention may be a single layered film or amulti-layered film composed of a plurality of layers. The single layeredfilm is preferable.

The in-plane retardation Re of the retardation film of this invention atwavelength of 550 nm is preferably 10 to 200 nm, and more preferably 10to 150 nm.

The first retardation film of this invention preferably has an Nz valueof 0.3 to 0.9, and more preferably 0.3 to 0.7. The second retardationfilm of this invention preferably has an Nz value of −0.29 to 0.29, morepreferably −0.2 to 0.2, and in particular preferably −0.15 to 0.15.

Now, Nz=(nx−nz)/(nx−ny) holds, where nx represents refractive index inthe in-plane slow axis direction, ny represents refractive index in thein-plane direction normal to nx, and nz represents refractive index inthe direction normal to nx and ny.

The thickness of the retardation film of this invention is typically,but not specifically limited to, 10 μm or less, more preferably 5 μm orless, and even more preferably 3 μm or less. The lower limit ofthickness is typically, but not specifically limited to, 10 nm or above,and preferably 50 nm or above.

The first retardation film of this invention may be formed by using acomposition which contains a polymer compound having a side chain, arod-like liquid crystal compound, and a photo-reactive compound. Themethod of manufacturing the film of this invention will be detailedlater.

The second retardation film of this invention may be formed by using acomposition which contains a polymer compound having certain side chain,and an alignment controlling agent. The method of manufacturing the filmof this invention will be detailed later.

<<Polymer Compound>>

The polymer compound used in this invention has a side chain whichcontains one or more azo groups and/or cynnamate groups, and 3 or moreand 10 or less arylene groups, and the side chain further has anoptionally substituted amino group, or hydrocarbon group at theterminal. The polymer compound means a compound having a weight averagemolecular weight of 10000 or more, and is preferably a polymerizedproduct of monomers.

The azo group is represented by —N═N—, and the cynnamate group isrepresented by —C₆H₄CH═CH—COO—. As a result of residence of one or moreazo groups and/or cynnamate groups, the polymer compound is allowed toparticipate in the photo-reaction. In this invention, upon irradiatedwith polarized ultraviolet radiation, the azo group and/or cynnamategroup induces dichroism due to cis-trans rearrangement, and thereby anoptically anisotropic retardation film may be obtained. When isomerizingthe polymer compound, by adding a step of heating in order to enhancethe reactivity, domains of several tens to several micrometers areformed, although not so large as domains of several tens micrometersever produced. The domains, possibly degrading the panel contrast, maybe suppressed from being produced, by adding a photo-reactive compoundwhich is highly compatible with the polymer. The present inventors alsofound that the refractive indices nx, ny and nz, which are known to varydepending on how the polymer compound aligns, may be varied by anadditive.

The polymer compound used in this invention has a side chain which has 3or more and 10 or less arylene groups, and the side chain further has anoptionally substituted amino group, or hydrocarbon group at theterminal. The thus bound arylene moiety is structurally rigid, thenumber of which contributes the optical performance expression andthermal reactivity, wherein the range of “3 or more and 10 or less” is asuitable range for both properties. The amino group or hydrocarbon groupat the terminal acts to enhance the optical performance expression whenthe polymer compound aligns, as compared with the case without aminogroup or hydrocarbon group.

The side chain preferably has one or more azo groups. The side chainmore preferably has 3 or more and 8 or less arylene groups, and evenmore preferably has 4 or more and 7 or less arylene groups.

The side chain has an amino group or hydrocarbon group at the terminal.The amino group may be unsubstituted or may have a substituent, andpreferably has a substituent. The substituent is exemplified by alkylgroup having 1 to 10 carbon atoms (preferably having 1 to 5 carbonatoms, and in particular preferably having 1 to 3 carbon atoms), andalkoxy group having 1 to 9 carbon atoms (preferably having 1 to 4 carbonatoms, and in particular preferably having 1 or 2 carbon atoms). Thesubstituent on the amino group is preferably alkyl group having 1 to 10carbon atoms (preferably having 1 to 5 carbon atoms, and in particularpreferably having 1 to 3 carbon atoms). The alkyl groups may mutuallycombine to form a ring.

The hydrocarbon group is an alkyl group, alkenyl group or alkynyl grouppreferably having 1 to 20 carbon atoms, more preferably 3 to 20 carbonatoms, even more preferably 3 to 10 carbon atoms, and yet morepreferably 3 to 7 carbon atoms, and may have any form of straight chain,branched chain, cyclic structure, and combination of them.

The polymer compound is exemplified by those of terminal connection typehaving the side chain which is bound at the terminal thereof, through aspacer or single bond, to the principal chain; and those of sideconnection type having the side chain which is bound inside thereof(laterally), through a spacer to the principal chain.

The terminal-connection-type polymer compound is preferably a compoundrepresented by Formula IX below.

In the formula, R¹ represents a hydrogen atom or methyl group.

In the formula, L represents a single bond, —(CH₂)_(x)O— (x is aninteger of 2 to 10, preferably 2 to 6), or —(CH₂CH₂O)_(y)— (y is aninteger of 1 to 5, preferably 1 to 3). —(CH₂)_(x)O— is preferable.

In the formula, R² represents an optionally substituted amino group, orhydrocarbon group.

In the formula, M represents a structure represented by Formula X below.

In the formula, each * represents a bonding site with L or R²; Yrepresents an azo group, —OCO—, —CO(═O)—, —OCO—CH═CH— or —CH═CH—CO₂—, mrepresents an integer of 2 to 9, the plurality of (Y)s may be same ordifferent; and Ar represents an optionally substituted arylene group(preferably a phenylene group).

The polymer compound represented by Formula IX is preferably exemplifiedby a polymer compound represented by Formula (IX-a) below.

In the formula, all symbols same as those used in Formula IX aresynonymous, and defined by the same preferable ranges.

In the formula, m1 represents 1 or 2, and m2 represents 1 or 2.

Each of R^(a), R^(b) and R^(c) independently represents a substituent(preferably, alkyl group having 1 or 2 carbon atoms, or halogen atom(preferably fluorine atom or chlorine atom)).

Each of x, y, and z independently represents an integer of 0 to 4, andpreferably 0.

Preferable examples of the polymer represented by Formula IX aboveinclude polymers represented by Formulae (IX-b) and (IX-c) below, whichcontain —OCO—CH═H— group or —CH═CH—CO₂— group for Y.

In the formula, all symbols same as those used in Formula IX aresynonymous, and defined by the same preferable ranges.

In the formula, m1 represents an integer of 0 to 2, and m2 represents aninteger of 1 or 2. Each of R^(a), R^(b) and R^(c) independentlyrepresents a substituent (preferably, alkyl group having 1 or 2 carbonatoms, or halogen atom (preferably, fluorine atom, chlorine atom)); andeach of x, y and z independently represents an integer of 0 to 4.

The side connection type polymer compound is preferably a compoundrepresented by Formula XI below.

In the formula, R¹ represents a hydrogen atom or methyl group.

In the formula, L represent a single bond, —(CH₂)_(x)O— (x is an integerof 2 to 10, and preferably 2 to 6) or —(CH₂CH₂O)_(y)— (y is an integerof 1 to 6, and preferably 3 to 6).

In the formula, each of R² and R³ independently represents a hydrogenatom, alkyl group having 1 to 10 carbon atoms (preferably having 1 to 5carbon atoms, and in particular preferably 1 to 3), alkoxy group having1 to 9 carbon atoms (preferably 1 to 4 carbon atoms, and in particularpreferably 1 or 2), or optionally substituted amino group.

In the formula, each of Y¹ and Y² independently represents an azo group,—OCO—CH═CH— or —CH═CH—CO₂—, and each of m1 and m2 independentlyrepresents an integer of 1 or 2. When m1 or m2 represents 2, theplurality of (Y¹)s or (Y²)s may be same or different.

As for methods of synthesizing the polymer compound, those described forexample in Jikken Kagaku Koza, in Japanese, “The Series of ExperimentalChemistry”, (4th Ed., No. 28, Kobunshi Gosei, in Japanese, “PolymerSynthesis”, p. 120-160) may be referred to.

The polymer compound is exemplified by compounds described in paragraphs[0053] to of JP-A-2011-237513. Among them, those having no cyano groupat the terminal of the side chain are preferably used in this invention.

The weight average molecular weight of the polymer compound ispreferably, but not specifically limited to, 10000 to 100000, morepreferably 10000 to 50000, and even more preferably 10000 to 30000.

The content of the polymer compound in the first retardation film ofthis invention is preferably 30 to 99% by mass, more preferably 50 to95% by mass, and most preferably 71 to 95% by mass. A single species ofthe polymer compound may be used independently, or two or more speciesmay be used in combination. When two or more species are used, the totalcontent preferably satisfies the contents described above.

The content of the polymer compound in the second retardation film ofthis invention is 71% by mass or more, preferably 75% by mass or more,more preferably 80% by mass or more, and even more preferably 90% bymass or more. The upper limit of the content of polymer compound ispreferably 99.9% by mass or below, more preferably 99% by mass or below,and even more preferably 97% by mass or below. When two or more speciesare used in combination, the total content preferably satisfies thecontents described above.

<<Rod-Like Liquid Crystal Compound>>

The rod-like liquid crystal compound was found to be enhanced in theretardation expression under the same conditions of manufacturing.Although the mechanism remains partially unclear, the present inventorssuppose that the rod-like liquid crystal compound assists thephoto-alignment of the polymer compound. Too much addition of therod-like liquid crystal compound will, however, degrade the panelcontrast due to self-alignable nature of liquid crystal, so that theamount of addition may be controlled within a suitable range.

The rod-like liquid crystal compound suitably used includes azomethines,azoxys, cyanobiphenyls, cyanophenyl esters, benzoic esters, phenylcyclohexane carboxylates, cyanophenylcyclohexanes, cyano-substitutedphenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes,tolans and alkenylcyclohexylbenzonitriles. The rod-like liquid crystalcompound is preferably polymerizable rod-like liquid crystal compoundhaving a polymerizable group, but may alternatively be rod-like liquidcrystal compound having no polymerizable group. The rod-like liquidcrystal compound is, in particular, preferably a compound having astructure represented by Formula (I) below.

Formula (I):

Q1-SP1-X1-M₁-(Y1-L-Y2-M₂)n-X2-SP2-Q2

In the formula,n is an integer of 0 or more, which denotes the number of repetition of(Y1-L-Y2-M₂),each of Q1 and Q2 represents a polymerizable group,each of SP1 and SP2 represents a straight-chain or branched alkylenegroup, or a group composed of a straight-chain or branched alkylenegroup combined with at least one of —O— and —C(═O)—, having a totalnumber of carbon atoms of 2 to 8 in integer;each of X1 and X2 represents a single bond or oxygen atom;—Y1-L-Y2- represents a straight-chain alkylene group, or a groupcomposed of straight-chain alkylene group and —O— and/or —C(═O)—, havinga total number of carbon atoms of 3 to 18 in integer; andeach of M₁ and M₂ configures a mesogenic group. In this specification,the mesogenic group means a group having a rod-like or plate-like rigidstructure (aromatic ring, etc.).M₁ is a group represented by

—Ar1-COO—Ar2-COO—Ar3-COO—

or

—Ar1-COO—Ar2-COO—Ar3-

or

—Ar1-COO—Ar2-Ar3-;

M₂ is a group represented by

—Ar3-OCO—Ar2-OCO—Ar1-OCO—

or

—Ar3-OCO—Ar2-OCO—Ar1-

or

—Ar3-OCO—Ar2-Ar1-; and

each of Ar1, Ar2 and Ar3 independently represents phenylene orbiphenylene substituted by an arbitrary number of bromine atom(s),methyl group(s), or methoxy group(s).

Each of the polymerizable groups Q1 and Q2 is preferably an acryloylgroup, methacryloyl group, radical polymerizable group (e.g., ethylenicunsaturated group) or ring-opened polymerizable group (e.g., epoxygroup, oxetane group), and more preferably an acryloyl group ormethacryloyl group.

Each of SP1 and SP2 represents a so-called spacer group, which is astructure for linking the polymerizable group and the mesogenic group.

The spacer group is preferably an alkylene group having 2 to 12 carbonatoms, or an alkylene oxide having 2 to 12 carbon atoms.

Each of X1 and X2 represents a linking group, and is selectable fromsingle bond and oxygen atom.

n represents an integer of 0 or more. Since increase in the value “n”means that a liquid crystal molecule contains a polymerized mesogenicgroups, so that an obtainable optically anisotropic layer will be lesslikely to shrink by polymerization when it is formed. n is preferably aninteger of 0 to 3, more preferably an integer of 0 to 2, and even morepreferably an integer of 0 or 1.

Each of Ar1, Ar2 and Ar3 independently represents phenylene orbiphenylene substituted by any number of bromine atom(s), methylgroup(s) or methoxy group(s). The total number of benzene ringscontained in Ar1, Ar2 or Ar3 is preferably an integer of 3 to 6, morepreferably an integer of 3 to 5, and in particular preferably an integerof 3 or 4.

Examples of the rod-like liquid crystal compound will be shown below,but not limited thereto.

<<Photo-Reactive Compound>>

The photo-reactive compound suitably used in this invention is acompound which is characterized by that an absolute value of differencebetween the SP (solubility parameter) value of the polymer compound andthe SP value of the photo-reactive compound is 1.1 or less, and which isreactive to light to initiate a polymerization reaction. Thephoto-reactive compound used in this invention preferably functions todisperse the polymer compound described above.

The SP value refers to solubility parameter, which may be calculated forlow-molecular substances by using the Hoy method suited to low-molecularsubstances, and for polymers by using the Hoy method suited to polymers.The absolute value of difference between the SP value of the polymercompound and the SP value of the photo-reactive compound is preferably1.1 or less, and the closer the value to zero, the better. By using aphoto-reactive compound having such SP value, the polymer compound andthe photo-reactive compound become more compatible, so that the polymercompound, if driven to form domains, will be interrupted by thephoto-reactive compound, and thereby the domains, which are causative ofdegradation in panel contrast, may be suppressed from growing.

Examples of the photo-reactive compound include acetophenones, benzoins,benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones,azo compounds, peroxides (JP-A-2001-139663, etc.), 2,3-dialkyldionecompounds, disulfide compounds, fluoroamine compounds, aromaticsulfoniums, lophin dimers, onium salts, borates, active esters, activehalogens, inorganic complexes, and coumarins

Examples of acetophenones include 2,2-dimethoxyacetophenone,2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxydimethyl p-isopropylphenyl ketone,1-hydroxycyclohexyl phenyl ketone,2-methyl-4-methylthio-2-morpholinopropiophenone,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone,4-phenoxydichloroacetophenone, and 4-t-butyl-dichloroacetophenone.

Examples of benzoins include benzoin, benzoin methyl ether, benzoinethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoinbenzenesulfonic ester, benzoin toluenesulfonic ester, benzoin methylether, benzoin ethyl ether and benzoin isopropyl ether.

Examples of benzophenones include benzophenone, hydroxybenzophenone,4-benzoyl-4′-methyldiphenyl sulfide, 2,4-dichlorobenzophenone,4,4-dichlorobenzophenone or p-chlorobenzophenone,4,4′-dimethylaminobenzophenone (Michler ketone), and3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone.

Borates are exemplified by organic borate compounds described, forexample, in official gazettes including JP-B2-2764769, JP-A-2002-116539and so forth, and Martin Kunz, “Rad Tech '98 Proceeding, April, p.19-22, 1998, Chicago”. They are exemplified by the compounds describedin paragraphs [0022] to [0027] of JP-A-2002-116539. Other organic boroncompounds are specifically exemplified by organoboron transition metalcoordination complexes typically described in JP-A-H06-348011,JP-A-H07-128785, JP-A-H07-140589, JP-A-H07-306527 and JP-A-H07-292014,and more specifically by ion complexes with cationic dye.

Examples of phosphine oxides include2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Examples of active esters include 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], sulfonic esters, and cyclic active ester compounds.More specifically, Compounds 1 to 21 described in EXAMPLE ofJP-A-2000-80068 are particularly preferable.

Examples of onium salts include aromatic diazonium salts, aromaticiodonium salts and aromatic sulfonium salts.

Active halogens are specifically exemplified by the compounds describedin Wakabayashi et al., Bull Chem Soc. Japan, Vol. 42, p. 2924 (1969),U.S. Pat. No. 3,905,815, JP-A-H05-27830, M. P. Hutt, Journal ofHeterocyclic Chemistry, Von (No. 3) (1970), and particularly by oxazolecompound substituted by trihalomethyl group, and s-triazine compound.More preferably, exemplified are s-triazine derivatives having at leastone mono-, di- or trihalogenated methyl group substituted on thes-triazine ring. Known specific examples include s-triazine andoxathiazole compound, such as2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,2-(p-styrylphenyl)-4,6-bis(trichloromethyl)-s-triazine,2-(3-bromo-4-di(ethylacetate)amino)phenyl)-4,6-bis(trichloromethyl)-s-triazine, and2-trihalomethyl-5-(p-methoxyphenyl)-1,3,4-oxadiazole. Particularlypreferable examples are those described in pages 14 to 30 ofJP-A-558-15503, pages 6 to 10 of JP-A-S55-77742, Compounds No. 1 to No.8 on page 287 of JP-B2-560-27673, Compounds No. 1 to No. 17 on pages 443to 444 of JP-A-560-239736, and Compounds Nos. 1 to 19 of U.S. Pat. No.4,701,399.

Examples of inorganic complexes include(η⁵-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)-phenyl)titanium.

Examples of coumarins include 3-ketocoumarin.

These initiators may be used independently, or as a mixture.

Commercially available photo-reactive compounds are exemplified byKayacure (registered trademark) (DETX-S, BP-100, BDMK, CTX, BMS, 2-EAQ,ABQ, CPTX, EPD, ITX, QTX, BTC, MCA, etc.) from Nippon Kayaku Co., Ltd.,Irgagure (registered trademark) (651, 184, 500, 819, 907, 369, 1173,1870, 2959, 4265, 4263, etc.) from BASF, and Esacure (registeredtrademark) (KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150, TZT) fromSartomer, Inc.

<Alignment Controlling Agent>

The alignment controlling agent used in this invention is a compoundwhich influences on the state of alignment when the polymer compound isphoto-aligned. As the alignment controlling agent, compounds having atleast two aromatic rings are preferably used. The “aromatic ring”includes not only aromatic hydrocarbon ring, but also aromaticheterocycle.

The aromatic hydrocarbon ring is preferably a 6-membered ring (i.e.,benzene ring). The aromatic heterocycle is typically an unsaturatedheterocycle. The aromatic heterocycle is preferably a 5-membered ring,6-membered ring or 7-membered ring, and more preferably a 5-memberedring or 6-membered ring. The heteroatom in the heterocycle is preferablya nitrogen atom, oxygen atom or sulfur atom, among which nitrogen atomis particularly preferable. Examples of the aromatic heterocycle includefuran ring, thiophene ring, pyrrole ring, oxazole ring, isooxazole ring,thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazanring, triazole ring, pyran ring, pyridine ring, pyridazine ring,pyrimidine ring, pyrazine ring and 1,3,5-triazine ring.

The aromatic hydrocarbon ring is preferably a benzene ring, condensedbenzene ring, or biphenyls.

As the aromatic ring, in particular 1,3,5-triazine ring is preferablyused.

More specifically, compounds typically disclosed in JP-A-2001-166144 arepreferably used.

The aromatic ring contained in the alignment controlling agentpreferably has 2 to 20 carbon atoms, more preferably 2 to 12, even morepreferably 2 to 8, and in particular preferably 2 to 6. In view of thenumber of ring-forming atoms, the aromatic ring is preferably a 5- to7-membered ring, and more preferably a 5-membered ring or 6-memberedring.

Modes of connection of two aromatic rings are classified into (a) a modeof forming a condensed ring, (b) a mode of direct connection through asingle bond, and (c) a mode of connection through a linking group(aromatic ring cannot form a spiro union). The modes of connection maybe any of (a) to (c).

Examples of the (a) condensed ring (condensed ring formed by two or morearomatic rings) include indene ring, naphthalene ring, azulene ring,fluorene ring, phenanthrene ring, anthracene ring, acenaphthylene ring,biphenylene ring, naphthacene ring, pyrene ring, indole ring, isoindolering, benzofuran ring, benzothiophene ring, indolizine ring,benzooxazole ring, benzothiazole ring, benzoimidazole ring,benzotriazole ring, purine ring, indazole ring, chromene ring, quinolinering, isoquinoline ring, quinolizine ring, quinazoline ring, cinnolinering, quinoxaline ring, phthalazine ring, pteridine ring, carbazolering, acrydine ring, phenanthridine ring, xanthene ring, phenazine ring,phenothiazine ring, phenoxathiine ring, phenoxazine ring and thianthrenering. Naphthalene ring, azulene ring, indole ring, benzooxazole ring,benzothiazole ring, benzoimidazole ring, benzotriazole ring andquinoline ring are preferable.

The single bond in (b) is preferably a bond between carbon atoms of twoaromatic rings. Two or more single bonds may combine two aromatic ringsto form, between the two aromatic rings, an aliphatic ring ornon-aromatic heterocycle.

Also the linking group in (c) is preferably bound to carbon atoms of twoaromatic rings. The linking group is preferably an alkylene group,alkenylene group, alkynylene group, —CO—, —O—, —NH—, —S— or combinationof them. Examples of linking group based on the combination will belisted below. Note that the examples of the linking group shown belowmay be laterally inverted.

c1: —CO—O—

c2: —CO—NH—

c3: -alkylene-O—

c4: —NH—CO—NH—

c5: —NH—CO—O—

c6: —O—CO—O—

c7: —O-alkylene-O—

c8: —CO-alkenylene-

c9: —CO-alkenylene-NH—

c10: —CO-alkenylene-O—

c11: -alkylene-CO—O-alkylene-O—CO-alkylene-

c12: —O-alkylene-CO—O-alkylene-O—CO-alkylene-O—

c13: —O—CO-alkylene-CO—O—

c14: —NH—CO-alkenylene-

c15: —O—CO-alkenylene-

Each of aromatic ring and linking group may optionally have asubstituent.

Examples of the substituent include halogen atom (F, Cl, Br, I), hydroxygroup, carboxy group, cyano group, amino group, nitro group, sulfogroup, carbamoyl group, sulfamoyl group, ureido group, alkyl group,alkenyl group, alkynyl group, aliphatic acyl group, aliphatic acyloxygroup, alkoxy group, alkoxycarbonyl group, alkoxycarbonylamino group,alkylthio group, alkyl sulfonyl group, aliphatic amido group, aliphaticsulfoamido group, aliphatic-substituted amino group,aliphatic-substituted carbamoyl group, aliphatic-substituted sulfamoylgroup, aliphatic-substituted ureido group and non-aromatic heterocyclicgroup.

The alkyl group preferably has 1 to 8 carbon atoms. Chain-like alkylgroup is preferred over cyclic alkyl group, and straight chain-likealkyl group is particularly preferable. The alkyl group may additionallyhave a substituent (e.g., hydroxy group, carboxy group, alkoxy group,alkyl-substituted amino group). Examples of the alkyl group (includingsubstituted alkyl group) include methyl group, ethyl group, n-butylgroup, n-hexyl group, 2-hydroxyethyl group, 4-carboxybutyl group,2-methoxyethyl group and 2-diethylamino ethyl group.

The alkenyl group preferably has 2 to 8 carbon atoms. Chain-like alkenylgroup is preferred over cyclic alkenyl group, and straight chain-likealkenyl group is particularly preferable. The alkenyl group mayadditionally have a substituent. Examples of the alkenyl group includevinyl group, allyl group and 1-hexenyl group.

The alkynyl group preferably has 2 to 8 carbon atoms. Chain-like alkynylgroup is preferred over cyclic alkynyl group, and straight chain-likealkynyl group is particularly preferable. The alkynyl group mayoptionally have a substituent. Examples of the alkynyl group includeethynyl group, 1-butynyl group and 1-hexynyl group.

The aliphatic acyl group preferably has 1 to 10 carbon atoms. Examplesof the aliphatic acyl group include acetyl group, propanoyl group andbutanoyl group.

The aliphatic acyloxy group preferably has 1 to 10 carbon atoms.Examples of the aliphatic acyloxy group include acetoxy group.

The alkoxy group preferably has 1 to 8 carbon atoms. The alkoxy groupmay additionally have a substituent (e.g., alkoxy group). Examples ofthe alkoxy group (including substituted-alkoxy group) include methoxygroup, ethoxy group, butoxy group and methoxyethoxy group.

The alkoxycarbonyl group preferably has 2 to 10 carbon atoms. Examplesof the alkoxycarbonyl group include methoxycarbonyl group andethoxycarbonyl group.

The alkoxycarbonylamino group preferably has 2 to 10 carbon atoms.Examples of the alkoxycarbonylamino group include methoxycarbonylaminogroup and ethoxycarbonylamino group.

The alkylthio group preferably has 1 to 12 carbon atoms. Examples of thealkylthio group include methylthio group, ethylthio group and octylthiogroup.

The alkylsulfonyl group preferably has 1 to 8 carbon atoms. Examples ofalkyl sulfonyl group include methanesulfonyl group and ethanesulfonylgroup.

The aliphatic amido group preferably has 1 to 10 carbon atoms. Examplesof the aliphatic amido group include acetamide.

The aliphatic sulfonamido group preferably has 1 to 8 carbon atoms.Examples of the aliphatic sulfonamido group include methanesulfonamidogroup, butanesulfonamido group and n-octanesulfonamido group.

The aliphatic-substituted amino group preferably has 1 to 10 carbonatoms. Examples of the aliphatic-substituted amino group includedimethylamino group, diethylamino group and 2-carboxyethylamino group.

The aliphatic-substituted carbamoyl group preferably has 2 to 10 carbonatoms. Examples of the aliphatic-substituted carbamoyl group includemethylcarbamoyl group and diethylcarbamoyl group.

The aliphatic-substituted sulfamoyl group preferably has 1 to 8 carbonatoms. Examples of the aliphatic-substituted sulfamoyl group includemethylsulfamoyl group and diethylsulfamoyl group.

The aliphatic-substituted ureido group preferably has 2 to 10 carbonatoms. Examples of the aliphatic-substituted ureido group includemethylureido group.

Examples of the non-aromatic heterocyclic group include piperidino groupand morpholino group.

The alignment controlling agent preferably has a molecular weight of 300to 800.

The alignment controlling agent is preferably represented by Formula (I)below.

In Formula (I):

each R²⁰¹ independently represents an aromatic hydrocarbon ring or aheterocycle, which has substituent(s) at least on any of the ortho, metaand para positions.

Each X²⁰¹ independently represents a single bond or —NR²⁰²—. Each R²⁰²independently represents a hydrogen atom, or alkyl group, alkenyl group,aromatic hydrocarbon cyclic group or heterocyclic group, which may besubstituted or unsubstituted.

The aromatic hydrocarbon ring represented by R²⁰¹ is preferably a phenylgroup or naphthyl group, wherein phenyl group is particularlypreferable. The aromatic hydrocarbon ring represented by R²⁰¹ may haveat least one substituent at any position of substitution. Examples ofthe substituent include halogen atom, hydroxy group, cyano group, nitrogroup, carboxy group, alkyl group, alkenyl group, aromatic hydrocarboncyclic group, alkoxy group, alkenyloxy group, aryloxy group, acyloxygroup, alkoxycarbonyl group, alkenyloxycarbonyl group, aryloxycarbonylgroup, sulfamoyl group, alkyl-substituted sulfamoyl group,alkenyl-substituted sulfamoyl group, aryl-substituted sulfamoyl group,sulfonamido group, carbamoyl group, alkyl-substituted carbamoyl group,alkenyl-substituted carbamoyl group, aryl-substituted carbamoyl group,amido group, alkylthio group, alkenylthio group, arylthio group and acylgroup.

The heterocyclic group represented by R²⁰¹ preferably shows aromaticity.In most cases, heterocycles showing aromaticity are unsaturatedheterocycles, preferably having the largest possible number of doublebonds. The heterocycle is preferably a 5-membered ring, 6-membered ringor 7-membered ring, more preferably 5-membered ring or 6-membered ring,and even more preferably 6-membered ring. The heteroatom in theheterocycle is preferably nitrogen atom, sulfur atom or oxygen atom, andin particular preferably nitrogen atom. The heterocycle showingaromaticity is, in particular, preferably pyridine ring (2-pyridyl or4-pyridyl group, in terms of heterocyclic group). The heterocyclic groupmay have a substituent. Examples of the substituents of the heterocyclicgroup are same as those of the aromatic hydrocarbon ring describedabove.

When X²⁰¹ represents a single bond, the heterocyclic group preferablyhas a free valence on the nitrogen atom. The heterocyclic group having afree valence on the nitrogen atom is preferably 5-membered ring,6-membered ring or 7-membered ring, more preferably 5-membered ring or6-membered ring, and in particular preferably 5-membered ring. Theheterocyclic group may have a plurality of nitrogen atoms. Theheterocyclic group may also have a heteroatom (e.g., 0, S) other thannitrogen atom. Examples of the heterocyclic group having a free valenceon the nitrogen atom will be listed below. Now —C₄H₉ ^(n) representsn-C₄H₉.

The alkyl group represented by R²⁰² may be a cyclic alkyl group or achain-like alkyl group, wherein chain-like alkyl group is preferable,and straight chain-like alkyl group is preferred over branchedchain-like alkyl group. The alkyl group preferably has 1 to 30 carbonatoms, more preferably has 1 to 20 carbon atoms, even more preferably 1to 10, yet more preferably 1 to 8, and most preferably 1 to 6. The alkylgroup may have a substituent. Examples of the substituent includehalogen atom, alkoxy group (e.g., methoxy group, ethoxy group) andacyloxy group (e.g., acryloyloxy group, methacryloyloxy group).

The alkenyl group represented by R²⁰² may be a cyclic alkenyl group or achain-like alkenyl group, wherein chain-like alkenyl group ispreferable, and straight chain-like alkenyl group is preferred overbranched chain-like alkenyl group. The alkenyl group preferably has 2 to30 carbon atoms, more preferably has 2 to 20 carbon atoms, even morepreferably 2 to 10, yet more preferably 2 to 8, and most preferably 2 to6. The alkenyl group may have a substituent. Examples of the substituentare same as those of the alkyl group descried above.

The aromatic hydrocarbon cyclic group and the heterocyclic grouprepresented by R²⁰² are same as the aromatic hydrocarbon ring and theheterocycle represented by R²⁰¹. The preferable ranges are the same asthose for the aromatic hydrocarbon ring and the heterocycle representedby R²⁰¹. The aromatic hydrocarbon cyclic group and the heterocyclicgroup may additionally have a substituent. Examples of the substituentare same as those of the aromatic hydrocarbon ring and the heterocyclerepresented by R²⁰¹.

The compound represented by Formula (I) may be synthesized typically byany of the known methods, including a method described, for example, inJP-A-2003-344655. The alignment controlling agent is detailed in JIPIIJournal of Technical Disclosure No. 2001-1745, p. 49. The agent isdescribed as an optical performance expressing agent in the publicationof application described above.

The content of the alignment controlling agent in the retardation filmof this invention, relative to 100 parts by mass of the polymercompound, is preferably 0.1 to 20 parts by mass, more preferably 1 to 20parts by mass, and even more preferably 1 to 15 parts by mass. Only onespecies of the alignment controlling agent may be used independently, ortwo or more species may be used in combination. When two or more speciesare used in combination, the total content preferably satisfies thecontent described above.

<Composition>

The composition of this invention (also referral to as “composition forretardation film”, hereinafter) contains the polymer compound, therod-like liquid crystal compound, and the photo-reactive compound.

The content of the polymer compound in the composition for retardationfilm, relative to the total solid content in the composition, ispreferably 30 to 99% by mass, more preferably 50 to 95% by mass, andmost preferably 71 to 95% by mass.

The content of the rod-like liquid crystal compound in the compositionfor retardation film, relative to 100 parts by mass of the polymercompound in the composition for retardation film, is preferably 0.1 to40 parts by mass, more preferably 1 to 20 parts by mass, and even morepreferably 3 to 10 parts by mass.

The content of the photo-reactive compound in the composition forretardation film, relative to 100 parts by mass of the polymer compoundin the composition for retardation film, is preferably 0.1 to 40 partsby mass, more preferably 1 to 20 parts by mass, and even more preferably3 to 15 parts by mass.

The composition of this invention (also referral to as “composition forretardation film”, hereinafter) contains the polymer compound, and thealignment controlling agent.

The content of the polymer compound in the composition for retardationfilm, relative to the total solid content in the composition, is 71% bymass or more, preferably 75% by mass or more, even more preferably 80%by mass or more, and yet more preferably 90% by mass or more. The upperlimit of content of the polymer compound is preferably 99.9% by mass orbelow, more preferably 99% by mass or below, and even more preferably97% by mass or below.

The content of the alignment controlling agent in the composition forretardation film, relative to 100 parts by mass of the polymer compoundin the composition for retardation film, is preferably 0.1 to 20 partsby mass, more preferably 1 to 20 parts by mass, and even more preferably1 to 15 parts by mass.

The composition of this invention may contain a solvent if necessary.Organic solvent is preferably used for the solvent. Examples of theorganic solvent include amide (e.g., N,N-dimethylformamide), sulfoxide(e.g., dimethyl sulfoxide), heterocyclic compound (e.g., pyridine),hydrocarbon (e.g., benzene, hexane), alkyl halide (e.g., chloroform,dichloromethane), ester (e.g., methyl acetate, butyl acetate), ketone(e.g., acetone, methyl ethyl ketone, cyclohexanone), and ether (e.g.,tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halide and ketone arepreferable. Two or more species of organic solvents may be used incombination. The amount of the solvent is preferably, but notspecifically limited to, 1 to 30% by mass and more preferably 1 to 10%by mass.

<Method of Manufacturing Retardation Film>

The method of manufacturing a retardation film of this inventionincludes at least a step of coating the above-described composition forretardation film on a substrate, and a step of photo-irradiating thecoated composition. It is preferable for the method of manufacturing aretardation film of this invention to further include a step of heatingthe composition, having been coated on the substrate, to 40° C. orabove, and a step of irradiating the heated composition with a polarizedlight at a dose of 300 to 30000 mJ/cm².

<<Step of Coating Composition for Retardation Film on Substrate>>

The composition for retardation film is preferably coated, for example,over the surface of a substrate such as polymer film, glass plate orquartz plate, and if necessary, over the surface of an alignment filmhaving been formed over the substrate. Preferable methods of coatinginclude spin coating, air knife coating, curtain coating, rollercoating, wire bar coating, gravure coating and die coating. Wire barcoating is preferable. The amount of coating is preferably controlled sothat a desired thickness of the retardation film may be manufactured.

<<Step of Heating Composition Coated on Substrate>>

The method of manufacturing of this invention preferably includes a stepof heating the composition having been coated in the step of coatingdescribed above. The step of drying may be implemented typically by amethod of heating the substrate, having the coated film (coatedcomposition) formed thereon, on a heated hot plate. The step of dryingmay alternatively be carried out by blowing the coated film with airheated to a predetermined temperature.

The heating temperature is preferably 40° C. or above, more preferably40 to 80° C., and even more preferably 50° C. to 70° C. The heating timeis preferably 5 seconds to 600 seconds, more preferably 5 seconds to 200seconds, and even more preferably 10 seconds to 100 seconds.

<<Step of Photo-Irradiating Coated Composition>>

In the step of photo-irradiation, the film formed on the substrate isirradiated with light.

The photo-irradiation may be given either by polarized light ornon-polarized light, wherein polarized light is preferably used, andlinear polarized light is more preferably used. Under photo-irradiationwith polarized light, polarizability of the film may be expressed, andthereby the retardation film with a controlled polarizability may bemanufactured.

The photo-irradiation with linear polarized light is an operation forinducing photo-reaction of the photo-reactive compound and the polymercompound having the azo group and/or cynnamate group. The wavelength oflight employed here varies depending on the photo-reactive compound tobe used, and is not specifically limited so long as it is necessary forphoto-reaction. The light used for the photo-irradiation preferably hasa peak wavelength in the range from 200 to 700 nm, and is preferably UVlight having a peak wavelength at 400 nm or shorter.

Means for obtaining the linear polarized light, suitably used here,include methods of using a polarizing plate (e.g., iodine polarizingplate, dichroic dye-containing polarizing plate, wire grid polarizingplate); methods of using a prism element (e.g., Glan-Thompson prism) orreflective polarizer based on Brewster's angle; and methods of usinglight emitted from intrinsically polarized laser source. Alternatively,only light of a necessary wavelength may selectively be irradiated,using a filter or wavelength conversion element.

Light source used for the photo-irradiation may be exemplified by thosewidely used, including lamps such as tungsten lamp, halogen lamp, xenonlamp, xenon flash lamp, mercury lamp, mercury-xenon lamp and carbon arclamp; various types of laser (e.g., semiconductor laser helium neonlaser, argon ion laser, helium cadmium laser, yttrium aluminum garnet(YAG) laser), light emitting diode, and cathode ray tube.

When the polymer compound is irradiated with linear polarized light, theazo group or the cynnamate group, whose long molecular axis beingaligned in parallel with the electric field vector, predominantlyabsorbs photons to cause trans-to-cis rearrangement, to thereby inducedichroism. The slow axis of the retardation layer in this process isaligned parallel to the linear polarized light.

The light is irradiated on the film normally or obliquely from the top,or from the back. The incident angle of light may vary depending onspecies of the photo-reactive compound or the polymer compound havingazo group(s) and/or cynnamate group(s), and is preferably 0 to 80° tothe surface of the polymer film, preferably 40 to 80°, and even morepreferably 50 to 70°.

The irradiation dose is preferably 300 to 30000 mJ/cm², and morepreferably 1000 to 20000 mJ/cm². By controlling the irradiation dose,the state of alignment of the azo groups or cynnamate groups in thepolymer compound may be changed, and thereby the Nz value of theretardation film may be controlled. In this invention, the retardationfilm having a desired Nz value may be manufactured, by controlling theirradiation dose depending on the Nz value required for the retardationfilm.

[Polarizing Plate]

The retardation film of this invention is useful, in particular, as aprotective film for polarizing plate. The polarizing plate of thisinvention may be manufactured by any of ordinary methods without speciallimitation. One known method is such as optionally treating theretardation film of this invention with an alkali, and bonding, using anadhesive, the film to the surface of a polarizer which is manufacturedby stretching a polyvinyl alcohol film while dipped in an iodinesolution. The adhesive is exemplified by polyvinyl alcohol-basedadhesive containing polyvinyl alcohol, polyvinyl butyral or the like;and vinyl-based latex containing butyl acrylate or the like.

The polarizing plate is configured by a polarizer and two polarizingplate protective films for protecting both surfaces of the polarizer.The retardation film of this invention may be used for at least one ofthe two polarizing plate protective films

<Liquid Crystal Display Device>

The liquid crystal display device of this invention has theabove-described retardation film, or the polarizing plate of thisinvention.

The liquid crystal display device is configured by a liquid crystal cellhaving a liquid crystal cell and two electrode substrates holding it inbetween, two polarizer plates disposed on both sides thereof, and atleast one retardation film disposed between the liquid crystal cell andeach polarizer. The liquid crystal layer of the liquid crystal cell istypically formed by injecting a liquid crystal, into a space formedbetween two substrates disposed while placing a spacer in between. Atransparent electrode layer is formed as a transparent film whichcontains an electro-conductive material, on the substrate. The liquidcrystal cell may additionally be provided with a gas bather layer, hardcoat layer, or under coat layer (used for bonding with the transparentelectrode layer). In most cases, these layers are provided on thesubstrate. The substrate of the liquid crystal cell is preferably 50 μmto 2 mm thick.

There are proposed various display modes including TN (Twisted Nematic),IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), AFLC(Anti-Ferroelectric Liquid Crystal), OCB (Optically Compensatory Bend),STN (Super Twisted Nematic), VA (Vertically Aligned), ECB (ElectricallyControlled Birefringence), and HAN (Hybrid Aligned Nematic). Alsoproposed are display modes using the above-described display modesimplemented in a multi-domain configuration. Among these modes, thisinvention is in particular suitably applicable to IPS-mode liquidcrystal display device. These liquid crystal display devices may be anyof transmission type, reflection type, and half-transmission type. Asfor the liquid crystal display devices, the description of paragraphs[0136] to [0142] of JP-A-2010-79239 may be referral to, the content ofwhich is incorporated into this specification.

This invention will be described in further detail, referring toExamples. The materials, amounts of use, ratios, details of processes,procedures of processes and so forth may suitably be modified withoutdeparting from the spirit of this invention. The scope of this inventionis therefore not limited to the specific examples described below.

EXAMPLES Example A <Manufacture of Alkali-Saponified TransparentSupport>

TD60UL (from FUJIFILM Corporation) was allowed to pass over an inductionheated roll at 60° C. to thereby elevate the film surface temperature upto 40° C., then coated on one surface with 14 ml/m² of an alkalinesolution having the composition below using a bar coater, heated to 110°C., and allowed to travel under a steam far infrared heater fromNoritake Co., Ltd. for 10 seconds. Then, 3 ml/m² of pure water wascoated again using a bar coater. After repeating rinsing with waterusing a fountain coater, and dewatering using an air knife three times,the film was transferred to a drying zone at 70° C. and allowed totravel for 10 seconds for drying. An alkali-saponified support was thusmanufactured.

Composition of Alkali Solution

Potassium hydroxide 4.7 parts by mass Water 15.8 parts by massIsopropanol 63.7 parts by mass Surfactant SF-1: C₁₄H₂₉O(CH₂CH₂O)₂₀H 1.0part by mass Propylene glycol 14.8 parts by mass

<Formation of Alignment Film>

On the alkali-saponified surface of the alkali-saponified support, acoating liquid for forming alignment film (A) having the compositionbelow was continuously coated using a #14 wire bar. The coating wasdried with a hot air at 60° C. for 60 seconds, and then with a hot airat 100° C. for 120 seconds. The degree of saponification of the modifiedpolyvinyl alcohol used here was found to be 96.8%.

Composition of Coating Liquid for Forming Alignment Film (A)

Modified polyvinyl alcohol (a/b/c = 12/88/0), 10 parts by mass shownbelow Water 308 parts by mass Methanol 70 parts by mass Isopropanol 29parts by mass Photo-polymerization initiator (Irgacure 0.8 parts by mass(registered trademark) 2959, from BASF)

<Preparation of Composition for Retardation Film> Example A1

One hundred parts by mass of Polymer Compound 1 below, 5 parts by massof Rod-Like Liquid Crystal Compound 1 below, 10 parts by mass ofPhoto-Reactive Compound 1 below (Irgacure (registered trademark) 907),and 775 parts by mass of methyl ethyl ketone were mixed to prepare acomposition for retardation film.

Examples A2 to A7, Comparative Examples A1 to A11

Compositions for retardation film were manufactured in the same way asin Example A1, except that the compounds used in Example A1 were changedto the compounds listed in Table below.

Absolute values of (SP value of polymer compound−SP value ofphoto-reactive compound) were listed in Table.

Polymer Compound 1: weight average molecular weight=24000

Polymer Compound 2: weight average molecular weight=22000

Polymer Compound 3: weight average molecular weight=14700

Polymer Compound 4: weight average molecular weight=28600

Polymer Compound 5: weight average molecular weight=44300

Polymer Compound 6: weight average molecular weight=14000

Rod-Like Liquid Crystal Compound 1

Discotic Liquid Crystal Compound 1

Discotic Liquid Crystal Compound 2

Photo-Reactive Compound 1 (Irgacure (registered trademark) 907, fromBASF)

Photo-Reactive Compound 2 (Irgacure 127, from BASF)

Photo-Reactive Compound 3

<Manufacture of Retardation Film> Example A1

A retardation film of Example A1 was manufactured according to themethod below

On the alignment film manufactured above, the composition forretardation film of Example A1 was coated using a bar coater, so as togive a dry film thickness of 0.4 μm. The coated film was conveyed underheating at 60° C. for 30 seconds in order to enhance mobility of thepolymer compound, and then exposed to ultraviolet radiation (UV) at 148mW through a polarizing plate, for a period of time the dose listed inTable may be reached. A retardation film of Example A1 was manufacturedin this way.

Comparative Example A1

A retardation film of Comparative Example A1 was manufactured accordingto the method below.

The alignment film manufactured above was continuously rubbed. In thisprocess, the longitudinal direction of the long film was alignedparallel to the feed direction, and an angle between the longitudinaldirection of the long film and the axis of rotation of a rubbing rollerwas set to 0°. Next, the composition for retardation film of ComparativeExample A1 was bar-coated on the thus rubbed alignment film so as togive a dry thickness of 0.6 μm. The film was then heated using a hot airat 130° C. for 150 seconds in order to dry off the solvent in thecoating liquid, and to align and ripen the liquid crystal compound, andirradiated by UV at 80° C. to fix the alignment of the liquid crystalcompound. A retardation film was manufactured in this way.

Comparative Example A2

A retardation film was manufactured by coating under the same conditionsas in Comparative Example A1, except that the composition forretardation film of Comparative Example A2 was used and the dry filmthickness was 0.6

Examples A2 to A7, Comparative Examples A3 to A11

Retardation films were manufactured by coating under the same conditionsas in Example A1, except that the dry film thickness and UV dose werechanged to those listed in Table, and that compositions for retardationfilm of Examples A2 to A7 and Comparative Examples A3 to A11 were used.

<Evaluation of Retardation Film> <<Re and Nz>>

Re and Nz at wavelength of 550 nm were measured using AxoScan fromAxometics, Inc. Results are summarized in Table.

<<Contrast>>

Contrast was evaluated by a method below.

Each retardation film was held between two polarizing plates, maximumluminance and minimum luminance were measured using a luminance meter(BMS, from Topcon Technohouse Corporation), and a film contrast valuewas obtained using Equation (1) below.

Film contrast value=1÷[1÷{(Minimum luminance of retardation filmdisposed between two polarizing plates in parallel Nicol state)÷(Minimumluminance of retardation film disposed between two polarizing plates incross Nicol state)}−1÷{(Minimum luminance observed through twopolarizing plates in parallel Nicol state without retardation film inbetween)÷(Minimum luminance observed through two polarizing plates incross Nicol state without retardation film in between)}]  Equation (1):

<Manufacture of Polarizing Plate>

Each of the retardation films manufactured in Examples and ComparativeExamples, and Fujitac (registered trademark) TD60UL (from FUJIFILMCorporation) were dipped in a 4.5 mol/L aqueous sodium hydroxidesolution (saponification liquid) conditioned at 37° C. for 1 minute,rinsed with water, further dipped in a 0.05 mol/L aqueous sulfuric acidsolution for 30 seconds, and allowed to pass through a water rinsingbath. Each film was dewatered three times using an air knife, thenallowed to stand in a drying zone at 70° C. for 15 seconds for drying,to thereby manufacture a saponified film.

A polyvinyl alcohol film of 120 m thick was immersed in an aqueoussolution containing 1 part by mass of iodine, 2 parts by mass ofpotassium iodide, and 4 parts by mass of boric acid, and stretchedfour-fold at 50° C., to thereby manufacture a polarizer.

The polarizer obtained above was held between two selected sheets of thesaponified films, and then bonded roll-to-roll using a 3% aqueous PVA(PVA-117H, from Kuraray Co., Ltd.) solution as an adhesive, whilealigning the polarization axis normal to the longitudinal direction offilm. Now, one of the polarizing films used here was any of the films ofExamples or Comparative Examples after saponified, and the other filmused here was Fujitac TD60UL which was saponified.

Note that, for the case where the retardation layer was formed by directcoating on the polarizing plate, followed by ripening, drying and UVirradiation, the step of manufacturing polarizing plate was omitted.

<Manufacture of Liquid Crystal Display Device>

A liquid crystal cell of iPad (registered trademark of Apple Inc.) wasused as an IPS-mode liquid crystal cell, after peeling off thepolarizing plate on the viewer's side.

In place of the thus-removed polarizing plate, each of the polarizingplates manufactured above was bonded to the liquid crystal cell, tomanufacture the individual liquid crystal display devices. In theprocess of bonding, the absorption axis of the polarizing plate and theoptical axis of the liquid crystal layer in the liquid crystal cell werealigned normal to each other, when the liquid crystal cell was observedin the direction normal to the substrate plane. Each of the thus bondedliquid crystal display device was illuminated to confirm that imageswere displayed without problems.

TABLE 1 Polymer Compound Liquid Number of Crystalline Photo-ReactiveCompound Photo- Arylene Compound SP value Reactive Terminal Groups inSpecies Species difference Species Group Group Side Chain (parts bymass) (parts by mass) from polymer Example A1 Polymer Azo Amino 4Rod-Like Photo-Reactive 1.0 Compound 1 Liquid Crystal Compound 1 (10)Compound 1 (5) Example A2 Polymer Azo Amino 4 Rod-Like Photo-Reactive1.0 Compound 1 Liquid Crystal Compound 1 (10) Compound 1 (5) Example A3Polymer Azo Alkyl 4 Rod-Like Photo-Reactive 1.0 Compound 2 LiquidCrystal Compound 1 (10) Compound 1 (5) Comparative None — — — Rod-LikePhoto-Reactive — Example A1 Liquid Crystal Compound 1 (10) Compound 1(100) Comparative None — — — Discotic Photo-Reactive — Example A2 LiquidCrystal Compound 1 (10) Compound 1 (100) Comparative Polymer Azo Amino 4None None — Example A3 Compound 1 Comparative Polymer Azo Amino 2Rod-Like Photo-Reactive — Example A4 Compound 3 Liquid Crystal Compound1 (10) Compound 1 (5) Example A4 Polymer Azo Amino 7 Rod-LikePhoto-Reactive  0.32 Compound 4 Liquid Crystal Compound 1 (10) Compound1 (5) Comparative Polymer Azo Amino 14  Rod-Like Photo-Reactive —Example A5 Compound 5 Liquid Crystal Compound 1 (10) Compound 1 (5)Comparative Polymer Azo Cyano 2 Rod-Like Photo-Reactive — Example A6Compound 6 Liquid Crystal Compound 1 (10) Compound 1 (5) Example A5Polymer Azo Amino 4 Rod-Like Photo-Reactive 1.0 Compound 1 LiquidCrystal Compound 1 (10) Compound 1 (5) Example A6 Polymer Azo Amino 4Rod-Like Photo-Reactive 1.0 Compound 1 Liquid Crystal Compound 1 (10)Compound 1 (5) Example A7 Polymer Azo Amino 4 Rod-Like Photo-Reactive1.0 Compound 1 Liquid Crystal Compound 1 (10) Compound 1 (5) ComparativePolymer Azo Amino 4 Rod-Like None — Example A7 Compound 1 Liquid CrystalCompound 1 (5) Comparative Polymer Azo Amino 4 Discotic Photo-Reactive1.0 Example A8 Compound 1 Liquid Crystal Compound 1 (10) Compound 1 (5)Comparative Polymer Azo Amino 4 Discotic Photo-Reactive 1.0 Example A9Compound 1 Liquid Crystal Compound 1 (10) Compound 2 (5) ComparativePolymer Azo Amino 4 Rod-Like Photo-Reactive 1.2 Example A10 Compound 1Liquid Crystal Compound 2 Compound 1 Comparative Polymer Azo Amino 4Rod-Like Photo-Reactive 1.4 Example A11 Compound 1 Liquid CrystalCompound 3 Compound 1 UV Irradiation Dry Film Conditions EvaluationThickness Illuminance Dose Re μm (mW/cm²) (mJ/cm²) (nm) Contrast NzExample A1 0.4 148 1480 83 110000 0.37 Example A2 0.7 148 1480 140100000 0.35 Example A3 0.4 148 1480 90 100000 0.75 Comparative 0.6 1481480 80 3500 1.0 Example A1 Comparative 0.4 148 1480 20 4500 1.48Example A2 Comparative 0.4 148 1480 50 40000 0.33 Example A3 Comparative0.4 148 1480 9 100000 0.35 Example A4 Example A4 0.4 148 1480 145 900000.40 Comparative 0.4 148 1480 75 3000 −0.5 Example A5 Comparative 0.4148 1480 5 120000 1.24 Example A6 Example A5 0.4 148 3900 145 1100000.85 Example A6 0.4 148 7800 145 110000 0.45 Example A7 0.4 148 15000145 110000 0.37 Comparative 0.4 148 1480 55 35000 0.3 Example A7Comparative 0.4 148 1480 40 44000 0.24 Example A8 Comparative 0.4 1481480 52 20000 0.23 Example A9 Comparative 0.4 148 1480 70 60000 0.35Example A10 Comparative 0.4 148 1480 65 40000 0.33 Example A11

Summary of Examples

The retardation films of Examples A1 to A7 which satisfy the conditionsof this invention and was manufactured using the polymer compounds, therod-like liquid crystal compound and the photo-reactive compound, werefound to achieve remarkably high levels of contrast in the state wherein-plane retardation was expressed, and also to achieve Nz=0.3 to 0.9.The retardation films of Comparative Examples A1 and A2, which did notcontain the polymer compound specified by this invention, failed toachieve Nz=0.3 to 0.9. The retardation film of Comparative Example A3,which contained neither the rod-like liquid crystal compound nor thephoto-reactive compound, showed only a low contrast. Comparative ExampleA5, having the number of arylene groups in the side chain of the polymercompound out of the range specified by this invention, showed only a lowcontrast, and failed to achieve Nz=0.3 to 0.9. Comparative Example A6,having a cyano group at the terminal of the side chain of the polymercompound, failed to express the in-plane retardation specified by thisinvention, and also failed to achieve Nz=0.3 to 0.9. The retardationfilm of Comparative Example A7 containing no photo-reactive compound,those of Comparative Examples A8 and A9 containing no rod-like liquidcrystal compounds, and those of Comparative Examples A10 and A11 havingthe SP values fallen outside the range of this invention showed only lowvalues of contrast. Comparative Examples A8 and A9 failed to achieveNz=0.3 to 0.9.

Example B <Manufacture of Alkali-Saponified Transparent Support>

TD60UL (from FUJIFILM Corporation) was allowed to pass over an inductionheated roll at 60° C. to thereby elevate the film surface temperature upto 40° C., then coated on one surface with 14 ml/m² of an alkalinesolution having the composition below using a bar coater, heated to 110°C., and allowed to travel under a steam far infrared heater fromNoritake Co., Ltd. for 10 seconds. Then, 3 ml/m² of pure water wascoated again using a bar coater. After repeating rinsing with waterusing a fountain coater, and dewatering using an air knife three times,the film was transferred to a drying zone at 70° C. and allowed totravel for 10 seconds for drying. An alkali-saponified support was thusmanufactured.

Composition of Alkali Solution

Potassium hydroxide 4.7 parts by mass Water 15.8 parts by massIsopropanol 63.7 parts by mass Surfactant SF-1: C₁₄H₂₉O(CH₂CH₂O)₂₀H 1.0part by mass Propylene glycol 14.8 parts by mass

<Formation of Alignment Film>

On the alkali-saponified surface of the alkali-saponified support, acoating liquid for forming alignment film (A) having the compositionbelow was continuously coated using a #14 wire bar. The coating wasdried with a hot air at 60° C. for 60 seconds, and then with a hot airat 100° C. for 120 seconds. The degree of saponification of the modifiedpolyvinyl alcohol used here was found to be 96.8%.

Composition of Coating Liquid for Forming Alignment Film (A)

Modified polyvinyl alcohol shown below 10 parts by mass (a/b/c =12/88/0) Water 308 parts by mass Methanol 70 parts by mass Isopropanol29 parts by mass Photo-polymerization initiator (Irgacure 0.8 parts bymass (registered trademark) 2959, from BASF)

<Preparation of Composition for Retardation Film> Example B1

One hundred parts by mass of Polymer Compound 1 below, 20 parts by massof Alignment controlling Agent 1 below, and 775 parts by mass of methylethyl ketone were mixed to prepare a composition for retardation film ofExample B1.

Polymer Compound 1: weight average molecular weight=24000

Alignment Controlling Agent 1

Comparative Example B1

Ninety-one parts by mass of Liquid Crystalline Compound 1 below, 5.2parts by mass of Low Molecular Compound 1 below, 0.09 parts by mass ofAlignment controlling Agent 2 below, 0.25 parts by mass of Alignmentcontrolling Agent 3 below, 3 parts by mass of Polymerization Initiator 1below, 1 part by mass of sensitizer below, and 775 parts by mass ofmethyl ethyl ketone were mixed to prepare a composition for retardationfilm of Comparative Example B1.

Liquid Crystalline Compound 1

Low Molecular Compound 1

Alignment controlling Agent 2 (B1365, a/b=92/8, from Wako Pure ChemicalIndustries, Ltd.)

Alignment controlling Agent 3 (B1258, a/b/c=25/25/50, from DICCorporation)

Photo-Polymerization Initiator: PM2215 (from BASF)

Sensitizer: PM758 (from Nippon Kayaku Co., Ltd.)

Comparative Example B2

Seventy-five parts by mass of Liquid Crystalline Compound 2 below, 25parts by mass of Liquid Crystalline Compound 3 below, 0.35 parts by massof Alignment controlling Agent 4 below, 3 parts by mass ofPhoto-Polymerization Initiator 1 above, 1 part by mass of sensitizerabove, and 775 parts by mass of methyl ethyl ketone were mixed, tothereby prepare a composition for retardation film of ComparativeExample B2.

Liquid Crystalline Compound 2

Liquid Crystalline Compound 3

Alignment controlling Agent 4 (B1279, a/b=32.5/67.5, from Wako PureChemical Industries, Ltd.)

<Manufacture of Retardation Film> Example B1

A retardation film of Example B1 was manufactured according to themethod below

On the alignment film manufactured above, the composition forretardation film of Example B1 was coated using a bar coater, so as togive a dry film thickness of 0.4 μm. The coated film was conveyed underheating at 60° C. for 30 seconds in order to enhance mobility of thepolymer compound, and then exposed to ultraviolet radiation (UV) at 148mW through a polarizing plate, for a period of time the dose listed inTable may be reached. A retardation film of Example B1 was manufacturedin this way.

Note that, while this Example uses the alignment film as a base, thefilm with equivalent performances may also be obtained by coating in thesame way, even on a glass substrate or on an ordinary polarizer.

Comparative Example B1

A retardation film of Comparative Example B1 was manufactured accordingto the method below.

The alignment film manufactured above was continuously rubbed. In thisprocess, the longitudinal direction of the long film was alignedparallel to the feed direction, and an angle between the longitudinaldirection of the long film and the axis of rotation of a rubbing rollerwas set to 0°. Next, the composition for retardation film of ComparativeExample B1 was bar-coated on the thus rubbed alignment film so as togive a dry thickness of 0.4 μm. The film was then heated using a hot airat 130° C. for 150 seconds in order to dry off the solvent in thecoating liquid, and to align and ripen the liquid crystal compound, andirradiated by UV at 80° C. to fix the alignment of the liquid crystalcompound. A retardation film was manufactured in this way.

Comparative Example B2

A retardation film was manufactured in the same way as in Example B1,except that the composition for retardation film of Comparative ExampleB2 was used and the condition was changed to include heating foralignment and ripening using a hot air at 60° C. for 150 seconds, and UVirradiation at 60° C.

Example B2

A retardation film was manufactured in the same way as in Example B1,except that the dry film thickness was changed to 1.5 μm.

Example B3

A retardation film was manufactured in the same way as in Example B1,except that the dry film thickness was changed to 2.8 μm.

Comparative Example B3

A retardation film was manufactured in the same way as in Example B1,except that the composition was prepared by changing the amount additionof Alignment controlling Agent 1 to zero parts by mass.

Example B4

A retardation film was manufactured in the same way as in Example B1,except that the amount of addition of Alignment controlling Agent 1 waschanged to 5 parts by mass.

Comparative Example B4

A retardation film was manufactured in the same way as in Example B1,except that the amount of addition of Alignment controlling Agent 1 waschanged to 45 parts by mass.

Comparative Example B5

A retardation film was manufactured in the same way as in Example B1,except that the amount of addition of Alignment controlling Agent 1 waschanged to 60 parts by mass.

Example B5

A retardation film was manufactured in the same way as in Example B1,except that the polymer compound was changed to Polymer Compound 2below, and that the dry film thickness was changed to 1.5 μm.

Polymer Compound 2: weight average molecular weight=28600

Comparative Example 6

A retardation film was manufactured in the same way as in Example B1,except that the polymer compound was changed to Polymer Compound 3below, and that the dry film thickness was changed to 2.8 μm.

Polymer Compound 3: weight average molecular weight=14700

Comparative Example B7

A retardation film was manufactured in the same way as in Example B1,except that the polymer compound was changed to Polymer Compound 4 below

Polymer Compound 4: weight average molecular weight=44300

Example B6

A retardation film was manufactured in the same way as in Example B1,except that the polymer compound was changed to Polymer Compound 5below, and that the dry film thickness was changed to 1.5 μm.

Polymer Compound 5: weight average molecular weight=22000

Comparative Example B8

A retardation film was manufactured in the same way as in Example B1,except that 75 parts by mass of Liquid Crystalline Compound 2 and 25parts by mass of Liquid Crystalline Compound 3 were used in place ofPolymer Compound 1, and that the amount of addition of Alignmentcontrolling Agent 1 was changed to 5 parts by mass.

<Evaluation of Retardation Film> <<Re and Nz>>

Re and Nz at wavelength of 550 nm were measured using AxoScan fromAxometics, Inc. Results are summarized in Table.

<<Contrast>>

Contrast was evaluated by a method below.

Each retardation film was held between two polarizing plates, maximumluminance and minimum luminance were measured using a luminance meter(BMS, from Topcon Technohouse Corporation), and a film contrast valuewas obtained using Equation (1) below.

Film contrast value=1÷[1÷{(Minimum luminance of retardation filmdisposed between two polarizing plates in parallel Nicol state)÷(Minimumluminance of retardation film disposed between two polarizing plates incross Nicol state)}−1÷{(Minimum luminance observed through twopolarizing plates in parallel Nicol state without retardation film inbetween)÷(Minimum luminance observed through two polarizing plates incross Nicol state without retardation film in between)}]  Equation (1):

<Manufacture of Polarizing Plate>

Each of the retardation films manufactured in Examples and ComparativeExamples, and TD60UL (from FUJIFILM Corporation) was dipped in a 4.5mol/L aqueous sodium hydroxide solution (saponification liquid)conditioned at 37° C. for one minute, and rinsed with water, dipped in a0.05 mol/L aqueous sulfuric acid solution for 30 seconds, and furtherallowed to pass through a rinsing water bath. The film was dewateredthree times using an air knife, then allowed to stand in a drying zoneat 70° C. for 15 seconds for drying. A saponified film was thusmanufactured.

A polyvinyl alcohol film of 120 μm thick was immersed in an aqueoussolution containing 1 part by mass of iodine, 2 parts by mass ofpotassium iodide, and 4 parts by mass of boric acid, stretched four-foldat 50° C., to thereby manufacture a polarizer.

The polarizer obtained above was held between two selected sheets of thesaponified films, and then bonded roll-to-roll using a 3% aqueous PVA(PVA-117H, from Kuraray Co., Ltd.) solution as an adhesive, whilealigning the polarization axis normal to the longitudinal direction offilm. Now, one of the polarizing films used here was any of the films ofExamples or Comparative Examples after saponified, and the other filmused here was Fujitac TD60UL which was saponified.

Note that, for the case where the retardation layer was formed by directcoating on the polarizing plate, followed by ripening, drying and UVirradiation, the step of manufacturing polarizing plate was omitted.

<Manufacture of Liquid Crystal Display Device>

A liquid crystal cell of iPad (registered trademark of Apple Inc.) wasused as an IPS-mode liquid crystal cell, after peeling off thepolarizing plate on the viewer's side.

In place of the thus-removed polarizing plate, each of the polarizingplates manufactured above was bonded to the liquid crystal cell, tomanufacture the individual liquid crystal display devices. In theprocess of bonding, the absorption axis of the polarizing plate and theoptical axis of the liquid crystal layer in the liquid crystal cell werealigned normal to each other, when the liquid crystal cell was observedin the direction normal to the substrate plane.

Each of the thus bonded liquid crystal display device was illuminated toconfirm that images were displayed without problems.

TABLE 2 Alignment controlling Dry Polymer Compound Liquid Agent Film UVIrradiation Photo- Number Of Crystalline (parts by Thick- Illumi-Reactive Terminal Arylene Compound mass) ness nance Dose Re EvaluationSpecies Group Group Groups Species Species μM mW/cm² mJ/cm² (nm)Contrast Nz Example B1 Polymer Azo Amino 4 None Alignment 0.4 148 148020 320000 −0.1 Compound controlling 1 Agent 1 (20) Comparative None — —— Liquid Alignment 0.4 148 1480 20 4500 1.48 Example B1 Crystallinecontrolling Compound Agent 2 1 And 3 (0.34 In Total) Comparative None —— — Liquid Alignment 0.4 148 1480 15 4800 1.0 Example B2 Crystallinecontrolling Compounds Agent 4 2, 3 (0.35) Example B2 Polymer Azo Amino 4None Alignment 1.5 148 1480 70 260000 −0.1 Compound controlling 1 Agent1 (20) Example B3 Polymer Azo Amino 4 None Alignment 2.8 148 1480 140240000 0 Compound controlling 1 Agent 1 (20) Comparative Polymer AzoAmino 4 None None 0.4 148 1480 50 40000 0.33 Example B3 Compound 1Example B4 Polymer Azo Amino 4 None Alignment 0.4 148 1480 40 280000−0.2 Compound controlling 1 Agent 1 (5) Comparative Polymer Azo Amino 4None Alignment 0.4 148 1480 5 540000 0 Example B4 Compound controlling 1Agent 1 (45) Comparative Polymer Azo Amino 4 None Alignment 0.4 148 14802 630000 0 Example B5 Compound controlling 1 Agent 1 (60) Example B5Polymer Azo Amino 7 None Alignment 1.5 148 1480 140 240000 0 Compoundcontrolling 2 Agent 1 (20) Comparative Polymer Azo Amino 2 NoneAlignment 2.8 148 1480 8 500000 0 Example B6 Compound controlling 3Agent 1 (20) Comparative Polymer Azo Amino 14  None Alignment 0.4 1481480 70 3000 −0.5 Example B7 Compound controlling 4 Agent 1 (20) ExampleB6 Polymer Azo Alkyl 4 None Alignment 1.5 148 1480 145 230000 0.25Compound controlling 5 Agent 1 (20) Comparative None — — — LiquidAlignment 0.4 148 1480 12 4800 1.0 Example B8 Crystalline controllingCompounds Agent 1 2, 3 (5) Note: Contents of Polymer Compounds in theretardation film of Examples B1 to B6 are 71% by mass or more.

Summary of Examples

The retardation films of Examples B1 to B7, which satisfy the conditionsof this invention and was manufactured using the polymer compounds andthe alignment controlling agent were found to achieve remarkably highlevels of contrast in the state where in-plane retardation was expressedas compared with the conventional retardation films using liquidcrystalline compounds, and also to achieve Nz more closer to zero, whichhas conventionally been difficult to achieve. The retardation films ofComparative Examples B1, B2 and B8, which do not contain the polymercompound specified by this invention, were found to show only lowcontrasts, and failed to bring Nz close to zero. The retardation film ofComparative Example B3 containing no alignment controlling agent failedto bring Nz close to zero. The retardation films of Comparative ExamplesB4 and B5 failed to express the in-plane retardation specified by thisinvention. Comparative Example B6, having the number of arylene groupsin the side chain of the polymer compound out of the range specified bythis invention, failed to express e in-plane retardation specified bythis invention. The retardation film of Comparative Example B7, havingthe number of arylene groups in the side chain of the polymer compoundout of the range specified by this invention, showed only a lowcontrast, and failed to bring Nz closer to zero.

1. A retardation film comprising a polymer compound and an alignmentcontrolling agent, wherein the polymer compound has a side chain whichhas one or more azo groups and/or cynnamate groups and 3 or more and 10or less of arylene group, the side chain further has an optionallysubstituted amino group, or a hydrocarbon group at the terminal, acontent of the polymer compound in the retardation film is 71% by massor more, and an in-plane retardation of the film at wavelength of 550 nmis 10 nm or more and 200 nm or less.
 2. The retardation film of claim 1,wherein the polymer compound is a compound represented by Formula IX:

in the formula, R¹ represents a hydrogen atom or methyl group, Lrepresents a single bond, —(CH₂)_(x)O— or —(CH₂CH₂O)_(y)—, x is aninteger of 2 to 10, y is an integer of 1 to 5, R² represents anoptionally substituted amino group or hydrocarbon group, and Mrepresents a structure represented by Formula X below:

in the formula, each * represents a bonding site with L or R²; Yrepresents an azo group, —OCO—, —CO(═O)—, —OCO—CH═CH— or —CH═CH—CO₂—, mrepresents an integer of 2 to 9, the plurality of (Y)s may be same ordifferent; and Ar represents an optionally substituted arylene group. 3.The retardation film of claim 1, wherein the alignment controlling agentis a compound represented by Formula I below:

in the formula, each R²⁰¹ independently represents an aromatichydrocarbon ring or heterocycle having substituent(s) at least on any ofthe ortho, meta and para positions, each X²⁰¹ independently represents asingle bond or —NR²⁰²—, each R²⁰² independently represents a hydrogenatom, or alkyl group, alkenyl group, aromatic hydrocarbon cyclic groupor heterocyclic group, which may be substituted or unsubstituted.
 4. Theretardation film of claim 1, wherein a content of the alignmentcontrolling agent, relative to 100 parts by mass of the polymercompound, is 0.1 to 20 parts by mass.
 5. The retardation film of claim1, which is a single layered film.
 6. The retardation film of claim 1,which has an Nz value of −0.29 to 0.29; where, Nz=(nx−nz)/(nx−ny), nxrepresents refractive index in in-plane slow axis direction, nyrepresents refractive index in an in-plane direction normal to nx, andnz represents refractive index normal to nx and ny.
 7. The retardationfilm of claim 1, which has a thickness of 5 μm or less.
 8. A compositioncomprising a polymer compound and an alignment controlling agent,wherein the polymer compound has a side chain which has one or more azogroups and/or cynnamate groups, and 3 or more and 10 or less arylenegroups; the side chain further has an optionally substituted aminogroup, or a hydrocarbon group at the terminal; and a content of thepolymer compound in the composition is 71% by mass or more relative tothe total solid content.
 9. A method of manufacturing a retardation filmof claim 1, which comprises coating the composition of claim 8 over asubstrate.
 10. The method of manufacturing a retardation film accordingto claim 9, which further comprises heating the composition, having beencoated on the substrate, at 40° C. or above, and photo-irradiating thecomposition after heating at a dose of 300 to 30000 mJ/cm².
 11. Apolarizing plate comprising a polarizer, and the retardation film ofclaim
 1. 12. A liquid crystal display device comprising the retardationfilm of claim
 1. 13. The liquid crystal display device of claim 12,which is an IPS liquid crystal display device.